REVERSE REACTION SINTERING OF Si3N4/SiC COMPOSITES

ABSTRACT

A method of making a composite sintered silicon nitride/silicon carbide body, including mixing a predetermined amount of silicon nitride powder with a predetermined amount of silicon carbide powder, heat-treating the resultant mixed powder at a temperature of between about 800 and 1500 degrees Celsius in a substantially nitrogen sintering atmosphere, and producing a thin film of silica around individual silicon nitride and silicon carbide grains. The thin film of silica is useful in retarding the diffusion of oxygen to the silicon nitride particles, slowing their oxidation. The pressure of the sintering atmosphere is not substantially greater than atmospheric pressure.

CROSS-REFERENCE TO RELATED APPLICATIONS

This patent application claims priority to co-pending U.S. patent application Ser. No. 11/279,461, filed Apr. 12, 2006, which claimed priority to U.S. Provisional Patent Application Ser. No. 60,597,049, filed Nov. 7, 2005.

BACKGROUND OF THE INVENTION

Polycrystalline silicon nitride (Si₃N₄) bodies are becoming increasingly attractive as structural and mechanical materials due to their ability to provide high strength and durability under severe conditions, and especially under high temperature applications. Si₃N₄ is characterized by high heat resistance, mechanical strength, thermal shock resistance, wear resistance, chemical stability, and hardness. One reason that Si₃N₄ does not enjoy wider use is that Si₃N₄ green powder compacts or green bodies are inherently difficult to sinter.

Known processes for producing a sintered silicon nitride body typically require the use of a sintering aid, such as Y₂O₃, Al₂O₃, MgO, or the like, added to a raw material powder of silicon nitride and a high-pressure N₂ atmosphere or N₂/inert gas atmosphere under which the Si₃N₄ body is sintered. Typically, the sintering aids form a grain boundary liquid during sintering, and more typically this liquid includes SiO2, either contributed as an impurity present in the Si₃N₄ or generated by the oxidation of Si₃N₄ by oxygen present in the sintering atmosphere.

The grain boundary liquid thus serves as a sintering aid and forms a silica-based glass in grain boundaries. This glass aids in the densification of the silicon nitride powder green body and in the formation of a fine grain structure in the resulting sintered body. However, the relative amounts of O and N in the glass phase is an uncontrolled variable, and thus the composition of the glassy phase at the grain boundary is likewise uncontrolled and variable, resulting in density gradients in the sintered body and compositional gradients at the grain boundaries.

Various additives have been added to improve the mechanical strength of the sintered ceramic bodies to enable them to perform under severe conditions. Silicon carbide (SiC) has been found to provide increased resistance to oxidation and mechanical strength at high temperatures to Si₃N₄. However, sintered ceramics composites produced as described above from a mixture of silicon nitride and silicon carbide powders typically contain silicon carbide particles on the order of microns only in the grain boundaries of silicon nitride particles. Attempts have been made to prevent the segregation of SiC in the grain boundaries of the sintered body. For instance, a composite sintered body of silicon nitride and silicon carbide was made by mixing a silicon nitride powder with a fine silicon carbide powder having an average diameter of 0.03 μm and a specific surface area of 30 m²/g and an yttria to form a green body which was sintered at 1750-1900° C. in a pressurized nitrogen atmosphere of 1 MPa; the body was further subjected it to an HIP treatment at 1750° C. in a 100 MPa nitrogen atmosphere. However, such a technique requires a bimodal PSD in the starting mixture of Si₃N₄ and SIC powders, and thus it is impossible to achieve a uniform mixture, resulting in a sintered body with an uneven grain structure. Further, the bimodal PSD of the main constituent powders makes an even, uniform distribution of the yttria sintering aid unlikely, resulting in insufficient sinterability and poor mechanical strength in the resultant sintered body.

Another technique for the production of a Si₃N₄/SiC body involves mixing a silicon metal powder, a silicon carbide powder and a sintering aid powder, forming the mixture into a green body, sintering the green body in a nitrogen atmosphere to react the metallic silicon with nitrogen to form Si₃N₄ which functions to bond SiC particles, and then elevating the temperature to further sinter the body via the sintering aid. Because metallic silicon is used instead of a silicon nitride powder as a starting material, shrinkage during sintering is minimized. However, this technique suffers from the difficulty in uniformly nitriding the silicon metal from the surface to the core of the body, which typically results in at least some silicon metal unreacted inside the resulting sintered body.

Yet another technique involves heat-treating a mixture of an organosilicon polymer and silicon powder in a non-oxidizing atmosphere, such as N₂, and pulverizing it to form a silicacious powder characterized by a surface covered with an amorphous material consisting of silicon and carbon. The powder is formed into a green body and sintered in an N₂ atmosphere. However, as with the previously-descried technique, it is difficult to uniformly nitride the body from surface to interior.

Partially crystalline composite powders of silicon nitride and silicon carbide have been produced as starting materials, mixed with a sintering aid powder and formed into green bodies which have been heated to the 1400-1600 degree Celsius range for a first sintering/reaction step and then liquid phase sintered in the 1600-2300 degree Celsius range. However, the resulting sintered body typically suffers from the generation of pores and the deterioration of mechanical properties by decomposition of amorphous components. Further, full density cannot be achieved via this technique absent elevated gas-pressure during sintering. Also, since a sintering aid powder is mixed with the partially crystalline composite powder and then sintered, the dispersion of the sintering aid powder is typically uneven, resulting in segregation of the sintering aid and inconsistent density and other physical properties observed in the sintered body.

Finally, a process of manufacturing a composite powder for the manufacture of a composite sintered body of silicon nitride and silicon carbide includes the steps of mixing silicon metal powder and carbonaceous powder together, heating the resultant mixture in an inert gas atmosphere, such as nitrogen, at a temperature of 1,400 degrees Celsius to simultaneously carbonize and nitride the silicon metal powder. However, this technique suffers from the preferential formation of β-silicon nitride, making it difficult to increase the percentage of α-silicon nitride in the composite powder. Since β-silicon nitride tends to grow in a needle shape, the resultant powder is suffers from the anisotropic particle shapes and is thus difficult to compact or pulverize.

There thus remains a need for a technique for evenly sintering a Si₃N₄/SiC body to density that does not require a pressurized nitrogen atmosphere and/or excessively high firing temperatures, as both requirements greatly increase the expense of the process and, thus, the end product. The present invention addresses this need.

SUMMARY OF THE INVENTION

A silica film is produced around Si₃N₄ and SiC particles present in a green body via oxidation at high temperature and is relatively thin and stable, allowing for control of oxidation of the particles during sintering in air or other primarily nitrogen or inert gas mixture having a relatively minor oxygen component, and under standard atmospheric or slightly to moderately elevated pressures. The production of a quantity of active oxide allows for the avoidance of excessive oxidation and the simultaneous sintering of the body. The guiding principle is one of thermodynamics. Si₃N₄/SiC composites are thus feasible in terms of thermodynamics. Better sintering can be achieved via controlling the temperature ramp rate and atmosphere during the process of sintering. A typical sintering temperature range is about 800 to about 1500 degrees Celsius; more typically, the sintering range is between about 800 and about 1200 degrees Celsius, wherein control of oxidation of nitrogen and nitrogen-containing compounds may be maintained. Typically, the bodies are soaked at about 1200 degrees Celsius to avoid excessive decomposition of the nitride. Sintering below the high temperature of 1500 degrees Celsius allows for the so-produced compact Si₃N₄/SiC composite of better quality.

The microstructure of products which made by sintering SiC—Si₃N₄ blends in the above temperature ranges show:

-   -   1. The main composition of the matrix of SiC—Si₃N₄ system after         sintering are SiO2 and Si₂N₂O, and the Si₃N₄ in the matrix is         mostly decomposed; however, the compact strength is still high.     -   2. The main composition of the matrix of SiC—Si₃N₄—Si system         after sintering are SiO₂, Si₂N₂O and metallic silicon, the         crystal morphology of Si₂N₂O is fine and small, and the ratio of         remnant nitrogen is higher.     -   3. The main composition of the matrix of SiC—Si₃N₄—SiO₂ system         after sintered are SiO₂ and Si₂N₂O. The Si₂N₂O crystals on the         surface grow better, but Si₂N₂O crystals in the interior are         still present, but smaller. The compact strength is high and the         ratio of remnant nitrogen is higher.

One object of the present invention is to provide a method for sintering SiC—Si₃N₄ at ambient pressure and in air. Related objects and advantages of the present invention will be apparent from the following description.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graphical illustration of a plot of standard free energy vs. absolute temperature for several oxidation reactions within the silicon-carbon-oxygen-nitrogen system.

FIG. 2 is a graphical illustration of a plot of standard free energy vs. absolute temperature for several other oxidation reactions within the silicon-carbon-oxygen-nitrogen system.

FIG. 3 is a phase diagram of the Si—N—O system at 1800 Kelvin

FIG. 4 is a graphical illustration of a plot of standard free energy vs. absolute temperature for several sintering/oxidation reactions within the silicon-carbon-oxygen-nitrogen system.

FIG. 5 is a graphical illustration of a plot of standard free energy vs. Celsius temperature for several regular non-oxide materials.

FIG. 6 is an X-Ray diffraction pattern taken of the as-sintered surface of SiC/Si₃N₄ composite sample P1 prepared according to a first embodiment of the present invention.

FIG. 7 is an X-Ray diffraction pattern taken of the interior of sample P1.

FIG. 8 is an SEM photomicrograph of sample P1.

FIG. 9 is a graphic representation of an n ESA analysis of sample P1.

FIG. 10 is an X-Ray diffraction pattern taken of the as-sintered surface of SiC/Si₃N₄ composite sample P2 prepared according to a first embodiment of the present invention.

FIG. 11 is an X-Ray diffraction pattern taken of the interior of sample P2.

FIG. 12 is a first SEM photomicrograph of the surface region of sample P2.

FIG. 13 is a second SEM photomicrograph of a pore of sample P2.

FIG. 14 is a first SEM photomicrograph of the interior of sample P2.

FIG. 15 is a second SEM photomicrograph of the interior of sample P2.

FIG. 16 is an X-Ray diffraction pattern taken of the as-sintered surface of SiC/Si₃N₄ composite sample P3 prepared according to a first embodiment of the present invention.

FIG. 17 is an X-Ray diffraction pattern taken of the interior of sample P3.

FIG. 18 is a first SEM photomicrograph of the surface region of sample P3.

FIG. 19 is a second SEM photomicrograph of a surface region of sample P3.

FIG. 20 is a first SEM photomicrograph of the interior of sample P3.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

For the purposes of promoting an understanding of the principles of the invention and presenting its currently understood best mode of operation, reference will now be made to the embodiments illustrated in the drawings and specific language will be used to describe the same. It will nevertheless be understood that no limitation of the scope of the invention is thereby intended, with such alterations and further modifications in the illustrated device and such further applications of the principles of the invention as illustrated therein being contemplated as would normally occur to one skilled in the art to which the invention relates.

Oxidation of SiC

When SiC particles are exposed to an oxygen-containing environment at elevated temperatures, a surface film of SiO₂ may form on the SiC particles through the partial oxidation of the SiC. The SiO₂ film acts as a protective film preventing the complete oxidation of the SIC, since, unless the environment is very rich in oxygen, oxygen diffusion through the silica film is very slow, even at elevated temperatures. As the system typically contains, in addition to silicon carbide, metal silicon, carbon and silica, the actual reaction kinetics are influenced by the relative amounts of C, SiC, Si, and SiO₂.

In the above system, SiC is decomposed into SiO(g), and SiO(g) is further oxidized into SiO₂(s). The speed of decomposition and oxidation of SiC is a function of the composition of temperature and the sintering atmosphere. The reaction may be described thermodynamically as follows.

SiC(s)+O₂(g)=Si(s)+CO₂(g)

Δ_(r) G ^(θ) ₁=−318560−12.1{T}_(K)(J·mol⁻¹)  2.1

2SiC(s)+O₂(g)=2Si(s)+2CO(g)

Δ_(r) G ^(θ) ₂=−72772−196.2{T}_(K)(J·mol⁻¹)  2.2

⅔SiC(s)+O₂(g)=⅔SiO(g)+⅔CO₂(g)

Δ_(r) G ^(θ) ₃=−284610−59.4{T}_(K)(J·mol⁻¹)  2.3

2SiC(s)+O₂(g)=2SiO(g)+2C(s)

Δ_(r) G ^(θ) ₄=−64728−176.2{T}_(K)(J·mol⁻¹)  2.4

SiC(s)+O₂(g)=SiO(g)+CO(g)

Δ_(r) G ^(θ) ₅=−144740−175.1{T}_(K)(J·mol⁻¹)  2.5

SiC(s)+O₂(g)=SiO₂(s)+C(s)

Δ_(r) G ^(θ) ₆=−832680+166.6{T}_(K)(J·mol⁻¹)  2.6

⅔SiC(s)+O₂(g)=⅔SiO₂(s)+⅔CO(g)

Δ_(r) G ^(θ) ₇=−630033+53.1{T}_(K)(J·mol⁻¹)  2.7

½SiC(s)+O₂(g)=½SiO₂(s)+½CO₂(g)

Δ_(r) G ^(θ) ₈=−613600+82.8{T}K(J·mol⁻¹)  2.8

2C(s)+O₂(g)=2CO(g)

Δ_(r) G ^(θ) ₉=−224760−174.1{T}_(K)(J·mol⁻¹)  2.9

2CO(g)+O₂(g)=2CO₂(g)

Δ_(r) G ^(θ) ₁₀=−564350+172{T}_(K)(J·mol⁻¹)  2.10

2Si(s)+O₂(g)=2SiO(g)

Δ_(r) G ^(θ) ₁₁=−216710−154.1{T}_(K)(J·mol⁻¹)  2.11

2SiO(g)+O₂(g)=2SiO₂(s)

Δ_(r) G ^(θ) ₁₂=−1600600+509.5{T}_(K)(J·mol⁻¹)  2.12

SiC(s)=Si(s)+C(s)

Δ_(r) G ^(θ) ₁₃=75992−11.1{T}_(K)(J·mol⁻¹)  2.13

It is evident that the value of Δ_(r)G^(θ) in reaction 2.13 is positive between 1000 and 1800K, and thus the reaction cannot proceed. FIG. 1 is made according to the relation of Δ_(r)G^(θ) and temperature in the scope of 1000 and 1800K. Regarding FIG. 1, it can be seen that under the standard state or at an oxygen partial pressure of 0.1 Mpa, the value of Δ_(r)G^(θ) in all reactions within the scope of temperature are negative, so the reactions can proceed. Accordingly, the value of Δ_(r)G^(θ) in reaction 2.12 is the most negative, and those in reactions 2.6, 2.7, 2.8, and 2.9 also relatively large negative values; thus the oxidation of SiC will proceed according to these reactions, the products of which are mainly SiO₂ and the gases CO₂ and CO.

The oxidation of SiC is influenced by many factors, such as the reaction temperature, sintering atmosphere, the composition of binding agent and crystal structure, diffusion speed of the various species taking part in the reactions, the particle size of the SiC, the particle size distribution, and the like. The oxidation of SiC may be envisioned as a multi-phase reaction, with O₂ as a diffusing phase and SiC as a fixed phase. The oxidation process is thus dependent on the diffusion of O₂ to the SiC and the reaction of O₂ at the SiC interface. Assuming a body formed primarily of SiC particles, the oxygen arrives at the SiC particle surface by a diffusion mechanism and reacts, forming the film of SiO₂. Once the silica film is established, additional oxygen must pass through the silica film to reach the SiC interface to further react therewith; thus, the diffusion of oxygen through the silica film becomes rate limiting. Meanwhile, the gaseous species CO₂, CO and/or SiO that are likewise produced must pass through the silica film. In other words, CO₂, CO and/or SiO are emitted by reverse diffusion, which also influence the diffusion of oxygen to the SiC interface. Thus, beyond the initial forming of the silica film, the rate of the oxidation of SiC is mainly controlled by diffusion of the various gaseous species through the silica film. Thus the oxidation speed has close relationship with the structure of product layers, the degree of compaction of the body, the oxidation temperature and time, and the property of the diffusion matter. Additionally, the multi-crystal transformation from α-silica to β-silica also impacts the diffusion of O₂ therethrough as well as having an effect on the compaction of the body, thus influencing the oxidation rate of the SiC particles.

Oxidation of Si₃N₄

Si₃N₄ is a non-oxide, and is thus easily oxidized at high temperatures. The oxidation behavior of Si₃N₄ and its products are dependent upon the ambient oxygen partial pressure: under high oxygen partial pressures, the oxidation products of Si₃N₄ are mainly SiO₂ and N₂, along with small amounts of Si₂N₂O(g) and NO(g); under low oxygen partial pressures, the main oxidation products are solid SiO₂ and gaseous SiO, with small amounts of N₂(g). According to thermodynamics, the oxidation reactions of Si₃N₄ under high temperatures may be expressed as follows:

⅓Si₃N₄(s)+O₂(g)=SiO₂(s)+⅔N₂(g)

Δ_(r) G ^(θ) ₁=−657533+64.1{T}_(K)(J·mol⁻¹)  2.14

⅕Si₃N₄(s)+O₂(g)=⅗SiO₂(s)+⅘NO(g)

Δ_(r) G ^(θ) ₂=−322260+28.4{T}_(K)(J·mol⁻¹)  2.15

⅔Si₃N₄(s)+O₂(g)=2SiO(g)+ 4/3N₂(g)

Δ_(r) G ^(θ) ₃=285360−381.3{T}_(K)(J·mol⁻¹)  2.16

2/7Si₃N₄(s)+O₂(g)= 6/7SiO(g)+ 8/7NO(g)

Δ_(r) G ^(θ) ₄=225606−177.8{T}_(K)(J·mol⁻¹)  2.17

4/3Si₃N₄(s)+O₂(g)=2Si₂N₂O(s)+⅔N₂(g)

Δ_(r) G ^(θ) ₅=−842547+38.2{T}_(K)(J·mol⁻¹)  2.18

⅘Si₃N₄(s)+O₂(g)= 6/5Si₂N₂O(s)+⅘NO(g)

Δ_(r) G ^(θ) ₆=−424760+13{T}_(K)(J·mol⁻¹)  2.19

⅔Si₂N₂O(s)+O₂(g)= 4/3SiO₂(s)+⅔N₂(g)

Δ_(r) G ^(θ) ₇=−602080+79.6{T}_(K)(J·mol⁻¹)  2.20

SiO₂(s)=Si(s)+O₂(g)

Δ_(r) G ^(θ) ₈=908670−177.7{T}_(K)(J·mol⁻¹)  2.21

Si₃N₄(s)=3Si(s)+2N₂(g)

Δ_(r) G ^(θ) ₉=753100−340.8{T}_(K)(J·mol⁻¹)  2.22

2Si₂N₂O(s)=4Si(s)+2N₂(g)+O₂(g)

Δ_(r) G ^(θ) ₁₀=1834100−488.1{T}_(K)(J·mol⁻¹)  2.23

FIG. 2 expresses the relationship of Δ_(r)G^(θ) in the above reactions and temperature between 1000 and 1800 K. It can be seen in FIG. 2 that under the standard state or at the oxygen partial pressure of 0.1 Mpa, the value of Δ_(r)G^(θ) in reaction 2.21, 2.22, and 2.23 are all positive and thus the three reactions cannot proceed. Reaction 2.17 may proceed when the temperature exceeds 1269K; the value of Δ_(r)G^(θ) in the other reactions in this temperature range are all negative, and thus reactions 2.19 and 2.20 may proceed. Under high oxygen partial pressures, the oxidation of Si₃N₄ can occur basically according to the above four reactions, with the products being mainly SiO₂ and N₂. If the oxygen partial pressure is in the lower range, the gases of Si₂N₂O and NO may likewise be produced in significant quantities.

The relationship of condensed phase and gas phase in the Si— N—O system and the balanced oxygen partial pressure in gas phase may be expressed a follows:

Si(s)+O₂(g)=SiO₂(s)

lg(p _(O2) /p ^(θ))=−22.449  2.24

3Si(s)+2N₂(g)=Si₃N₄(s)

lg(p _(N2) /p ^(θ))=−4.341  2.25

4Si₃N₄(s)+3O₂(g)=6Si₂N₂O(s)+2N₂(g)

lg(p _(N2) /p ^(θ))= 3/2lg(p _(O2) /p ^(θ))+37.616  2.26

2Si₂N₂O(s)=4Si(s)+2N₂(g)+O₂(g)

lg(p _(N2) /p ^(θ))=−½lg(p _(O2) /p ^(θ))−18.326  2.27

2Si₂N₂O(s)+3O₂(g)=4SiO₂(s)+2N₂(g)

lg(p _(N2) /p ^(θ))= 3/2lg(p _(O2) /p ^(θ))+26.572  2.28

Si₃N₄(s)+3O₂(g)=3SiO₂(s)+2N₂(g)

lg(p _(N2) /p ^(θ))= 3/2lg(p _(O2) /p ^(θ))+29.333  2.29

From the above relationships, it can be seen that the reaction in the interface of Si₃N₄ and SiO₂ may proceed as follows, producing Si₂N₂O (FIG. 3):

4Si₃N₄(s)+3O₂(g)=6Si₂N₂O(s)+2N₂(g)

or Si₃N₄(s)+SiO₂(s)=2Si₂N₂O(s)

Oxidation of Si₂N₂O

Theoretically, Si₂N₂O may be totally oxidized under an oxidizing atmosphere (without the protection of the silica film) if the reaction is allowed to proceed for a sufficiently long time. Under the oxidizing atmosphere (i.e., a high oxygen partial pressure), the product of oxidation is mainly SiO₂ and the gas phase is mainly N₂ without substantial SiO gas. But under low oxygen partial pressure, the gas phases in the products of oxidation are mainly SiO gas and a little N₂. The above thermodynamics calculation results of equations 2.16 and 2.29 can be seen and as following equation 2.30:

⅓Si₃N₄(s)+O₂(g)=SiO₂(s)+⅔N₂(g)

Δ_(r) G ^(θ)=−663776.7+69.31{T}_(K)(J·mol⁻¹)  2.30

To sum up, the oxidation of Si₃N₄ can produce the different results according to the different temperature and oxygen partial pressure conditions. At high temperature and under an oxidizing atmosphere, the oxidation reactions of Si₃N₄ are as follows:

Si₃N₄(s)+3O₂(g)=3SiO₂(s)+2N₂(g)

4Si₃N₄(s)+3O₂(g)=6Si₂N₂O(s)+2N₂(g) and

2Si₂N₂O(s)+3O₂(g)=4SiO₂(s)+2N₂(g)

So the above reactions can proceed at high temperature and under oxidizing conditions. At high temperature and under low oxygen partial pressure, the oxidation reaction of Si₃N₄ is as follows:

Si3N4(s)+ 3/2O2(g)=3SiO(g)+2N2(g)

In addition to this, there is also

4Si3N4(s)+3O2(g)=6Si2N2O(s)+2N2(g)

which should be avoided during the sintering process.

The Si₃N₄/SiC System

In the Si₃N₄/SiC multi-phase system, in addition to above oxidation reactions of SiC and Si₃N₄, other reactions may occur, which are as follows:

SiO₂(s)+CO(g)=SiO(g)+CO₂(g)

Δ_(r) G ^(θ) ₁=517960−168.7{T}_(K)(J·mol⁻¹)  2.31

⅙Si₃N₄(s)+CO(g)=½SiO₂(s)+⅓N₂(g)+C

Δ_(r) G ^(θ) ₂=−21643+119.1{T}_(K)(J·mol⁻¹)  2.32

½SiC(s)+CO(g)=½SiO₂(s)+ 3/2C(s)

Δ_(r) G ^(θ) ₃=−304280+171.2{T}_(K)(J·mol⁻¹)  2.33

SiC(s)+CO₂(g)=SiO₂(s)+2C(s)

Δ_(r) G ^(θ) ₄=−437210+167.1{T}_(K)(J·mol⁻¹)  2.34

⅓Si₃N₄+CO₂(g)=SiO₂+C+⅔N₂(g)

Δ_(r) G ^(θ) ₅=−262+64.5{T}_(K)(J·mol⁻¹)  2.35

½SiO₂(s)+SiO(g)+N₂(g)=½Si₃N₄(s)+O₂(g)

Δ_(r) G ^(θ) ₆=186140+158.6T}_(K)(J·mol⁻¹)  2.36

3/2SiC(s)+N₂(g)=½Si₃N₄(s)+ 3/2C(s)

Δ_(r) G ^(θ) ₇=−262565+153.8{T}_(K)(J·mol⁻¹)  2.37

3/2SiO₂+N₂(g)=½Si₃N₄+ 3/2O₂(g)

Δ_(r) G ^(θ) ₈=984600−95.3{T}_(K)(J·mol⁻¹)  2.38

FIG. 4 illustrates the relationship of Δ_(r)G^(θ) in above reactions and temperature between 1000 and 1800K. FIG. 4 shows that under the standard state or at high oxygen partial pressure, only the value of Δ_(r)G^(θ) in reaction 2.34 within this temperature range is negative, and thus may proceed. Reaction 2.33 may proceed when the temperature is below 1778K, and reaction 2.37 may proceed when the temperature is below 1707K. For other five reactions, Δ_(r)G^(θ) is positive in the temperature range from 1000 to 1800K, and thus the reactions cannot proceed. In other words, from the point of view of thermodynamics, SiC may possibly be reacted with CO₂ and a little CO to produce SiO₂ and C; SiC may also be reacted with N₂ (produced by the oxidation of Si₃N₄) to produce Si₃N₄ and C. Certainly, C thus produced may be further oxidized into CO₂ and CO under the oxidizing atmosphere.

The Oxidizing Sequence of Si₃N₄ and SiC when Sintered.

Referring to FIG. 5, it can be seen that Si₃N₄ will be oxidized before SiC within the sintering temperature range. As discussed above, Si₃N₄ reacts with oxygen as expressed in reactions 2.30, 2.26 and 2.16, which may proceed depending on the oxygen partial pressure. From FIG. 3, it can be seen that when p_(O) ₂ is relatively low, Si₂N₂O is first produced, and the reaction product is SiO₂ with rising p_(O) ₂ . Regarding SiO, because it is a gaseous compound, the discussion may be carried out through the relationship of SiO and SiO₂.

$\begin{matrix} {{{{SiO}(g)} + {\frac{1}{2}{O_{2}(g)}}} = {{SiO}_{2}(s)}} & 2.39 \\ {{\Delta_{2}G^{\theta}} = {{- 812140} - {325.18\left\{ T \right\}_{K}\left( {J \cdot {mol}^{- 1}} \right)}}} & \; \\ {{\Delta_{r}G} = {{\Delta_{r}G^{\theta}} - {{RT}\; {{\ln \left( {p_{SiO}/p^{|É}} \right)} \cdot \left( {p_{O_{2}}/P^{\theta}} \right)^{1/2}}}}} & 2.40 \end{matrix}$

When p_(O) ₂ is higher, the negative value is increased, Δ_(r)G<0 and the reaction can be carried out toward the direction of producing SiO₂; when p_(O) ₂ is lower, Δ_(r)G>0 and SiO is produced. SiO is a gaseous compound and, once produced, can be volatilized out, especially when p_(O) ₂ is lower than convertible oxygen partial pressure. Thus, SiO can reach the outside pressure and be volatilized rapidly. In this process, SiO₂ is expected as the produced surface layer and SiO₂ or Si₂N₂O are at the inner particulate interface; SiO is not expected to form and be volatilized. Thus, the reactions must be carried out under higher p_(O) ₂ .

The Stability of the Surface Film of SiO₂

SiO₂ is in the compact contacting state with Si₃N₄ and SiC, so the reaction between them must be considered.

⅓Si₃N₄+SiO₂=2SiO(g)+⅔N₂(g)

Δ_(r) G ^(θ)=931363−442.25{T}_(K)(J·mol⁻¹)  2.41

Δ_(r) G=Δ _(r) G ^(θ)+RTln(p _(SiO) /p ^(¦E))²·(p _(N) ₂ /p ^(θ))^(2/3)   2.42

From reaction 2.44, it can be shown that 1 mol N₂ and 3 mol SiO are produced at same time, that is

p_(SiO) /p ^(¦E)=3p _(N) ₂ /p ^(θ) and

Δ_(r) G=Δ _(r) G ^(θ)+2RTln3+RTln(p _(N2) /p ^(θ))^(8/3)   2.43

and

Δ_(r) G=931363−423.98T+RTln(p _(N) ₂ /p ^(θ))^(8/3)2.44

are thus obtained.

If the production of gaseous SiO and N₂ is sufficient to break through the surface film of SiO₂, the sum of pressure of the two gases should be more than the atmospheric pressure, that is:

p_(SiO) /p ^(¦E) +p _(N) ₂ /p ^(θ)=1 and p _(SiO) /p ^(¦E)=3p _(N) ₂ /p ^(θ)  2.45

So p_(N) ₂ /p^(θ)=¼ is obtained and

Δ_(r) G=931363−454.71T  2.46

is obtained.

Thus the transition temperature of T=2048.26K=1775.03° C. can be obtained. That is, when the temperature is higher than this value, the gases of SiO and N₂ can break through the surface film of SiO₂, and the composite material cannot be protected. But if the sintering temperature of the process is lower than 1500° C., the surface film produced can protect the so-coated particle.

Because the surface film is covered on the composite material, it is also influenced by SiC. Thus the expression

SiC+2SiO₂=3SiO(g)+CO(g)  2.47

wherein the transition temperature of T=2048K=1775° C. is obtained, which indicates the surface film of SiO₂ can protect the composite material.

Another situation regarding the effect of the producing Si₂N₂O is likewise considered. When SiC exists, the oxygen partial pressure in the film is lower, and the possibility of producing Si₂N₂O is greater.

⅔Si₃N₄+SiO₂═Si₂N₂O+SiO(g)+⅓N₂(g)

Δ_(r) G ^(θ)=375332−236.06T  2.48

Δ_(r) G=A _(r) G ^(θ)+RTln_((pSiO)/p^(¦E) ₎·_((pN2)p^(θ))   2.49

The reaction here is also that 1 mol N₂ and 3 mol SiO are produced at the same time, so p_(SiO)/p^(¦E)=3p_(N) ₂ /p^(θ). The pressure which can break through the surface film is greater than atmospheric pressure, that is p_(SiO)/p^(543 E)+p_(N) ₂ /p^(θ)=1 and p_(N) ₂ /p ^(θ)=¼ is

obtained, and thus

Δ_(r) G=375332−241.46T  2.50

The transition temperature of T=1554.45K=1281.22° C. is obtained. That is, when Si₂N₂O is produced, the gas pressure of SiO and N₂ produced can break through the surface film at a relatively low temperature. But the Si₂N₂O can still form the protecting film. If the oxygen partial pressure is high enough to oxidize Si₂N₂O, then the protecting SiO₂ film is formed. This is also the basis of forming a Si₂N₂O/Si₃N₄/SiC system.

The Sintering Process of Reverse Reaction Sintering Si₃N₄SiC Composites

The sintering process of reverse reaction sintering Si₃N₄/SiC composites is actually the reaction process of controlling oxidation, by reacting to produce new and active SiO₂ and a little Si₂N₂O which segregates onto the SiC and Si₃N₄ particle surfaces, thus aiding in sintering. Additionally, the presence of impurities, to some extent, may be regarded sintering aids; for example clay, metal Si, SiO₂, and the like, may further assist in sintering.

The oxidation of reverse reaction sintering Si₃N₄/SiC composites is a function of such factors as the reaction temperature, the sintering atmosphere, the composition of binding agent and crystal structure, the particle size of raw material, the particle size distribution of the system, and the like. In this process, O₂ is a diffusing phase, SiC and Si₃N₄ are solid phases, and the oxidation process is limited by the diffusion of O₂ to the particle interfaces and the diffusion of reaction products away therefrom. Oxygen diffuses to the surface of the SiC and Si₃N₄ particles and forms a film of SiO₂ thereupon. To further react with a given particle, oxygen must first diffuse through the SiO₂ film to reach the reaction interface; the oxidation reaction is thus limited by the diffusion of oxygen through the silica shells that form on the respective particles. Likewise, the gaseous reaction products, such as CO₂, CO, SiO, N₂ and NO, and the like, are emitted by reverse diffusion from the interface through the silica layer, which also influences the diffusion of oxygen therethrough to the interface.

The driving force of sintering is the surface energy (surface tension). The powder material is typically highly dispersed, and more typically is characterized by an extremely large specific surface area, and thus has relatively high surface energy. As systems have a tendency to achieve the state of lowest energy, the reduction of surface free energy is the main driving force of sintering the material. The difference between the surface energy (ε_(b)) of powder particles and the interface energy (ε_(s)) of crystal particles of multi-crystal sinter will result in the reduction of free energy of system, and the ratio ε_(b)/ε_(s), is thus a measure of the sintering character of powder.

The first step of sintering process can be regarded as the compacting of the body formed of partially compacted particulate material, such as a mixture of SiC and S₃N₄ particles. During the initial period (wherein the temperature is below 800 degrees Celsius), the body is heated in the air and a thin silica layer is formed around substantially all of the particles; the silica layer thus prevents further oxidation of the silicaeous particles. As the temperature is increased, impurities in the raw material may be reacted with SiO₂ to produce a lower melting point eutectic material. Typically, the viscosity of eutectic liquid is relatively low and the particles making up the body may be redistributed by surface tension.

The second step of sintering process is typically one of dissolving-diffusing-reseparating out. During this step, the diffusion of O₂ through the silica layer limits the reaction rates. Due to the existence of the eutectic liquid, the speed of compacting the body is increased. After the particles are redistributed, they are separated by the thin liquid film. As the body densifies, the liquid separating the particles becomes quite thin. Typically, the thinner the liquid film, the greater the pressure of the particles. The solubility at the point of particles contacting is increased due to this pressure. The material at the contact points is gradually dissolved into the liquid, and then transferred to other surface and separated out.

The third step of sintering process is the process of grain growth. Due to the shrinkage/disappearance/closure of the pores, sintering speed is reduced but the microstructure of the material still continues to change. That is, other phenomena such as the grain growth, necking, and capillary action of liquid filing pores still continue to occur, but at slower rates. During the cooling process, the remaining interfacial liquid is hardened to glassy state or partially crystallized. If an exterior force is applied, the degree of compacting between the particles may be accelerated. As the thermodynamic equations illustrate, the sintering process is accompanied by the oxidation of Si₃N₄, which provides a continuous emission of N₂.

The Microstructure Analysis of Reverse Reaction Sintering Si₃N_SiC Composites

The study on microstructure of reverse reaction sintering Si₃N₄/SiC composites includes the study on the structure of micro minerals and of micro pores. The surface area and inner area of sample P1, P2, P3 and P4 were analyzed by XRD, SEM and EPMA in order to confirm the microstructure of the sintered samples. The result of the analyses are as follows:

The Study on Microstructure of SiC—Si₃N₄ Sintering System

Raw Particle Sample # P1 Materials Size(mm) (weight %) Sample # P2 Sample # P3 SiC 2.8-0.9  35 35 30 0.9-0.15 30 30 30 0.115 5 5 5 0.063 5 0.045 10 10 10 Si₃N₄ 0.088 15 15 15 SiO₂ 10 Si 5

Sample P1 was analyzed by XRD and SEM. FIGS. 6 and 7 are surface area (0-5 mm) and inner area (8-16 mm) XRD patterns, respectively. The samples were prepared by mixing the constituent powders and forming them into green bodies. This was done by pressing at about 105 MPa; some samples required small amounts of binder (dextrine solution) to allow pressing. The green bodies were dried at 105 degrees Celsius for 10 hours. The green bodies were then heated at a rate of 50 degrees Celsius/hour to about 800 degrees Celsius, where they were allowed to soak for 8 to 10 hours. The samples were then heated at a rate of 50 degrees Celsius/hour to about 1450 degrees Celsius, where they were allowed to soak for 5 hours. The samples were then cooled to room temperature. All sintering was done in air under normal atmospheric pressures.

FIG. 6 shows that the surface sample of P1 is one of 0-5 mm area and its main crystal phases are SiC, Si₃N₄ and SiO₂. FIG. 7 shows that the interior of sample of P1 is mainly composed of SiC, Si₃N₄ and SiO₂, but with more Si₃N₄ and less SiO₂ than at the surface. Thus, the sintering and oxidation of the system without a sintering agent yields SiC and Si₃N₄ dispersed in a primarily silica matrix.

FIGS. 8 and 9 relate to a nitrogen-containing oxide found in the section of sample P1 and its morphology. SEM and ESA show the existence of nitride in the state of conglomerate, indicating that Si₂N₂O is produced during the oxidation of Si₃N₄. The absence of the primary peak for Si₂N₂O in XRD pattern indicates that either the amount of Si₂N₂O present is relatively small, the Si₂N₂O is amorphous or glassy, or the Si₂N₂O crystal structure includes sufficient impurities so as to be substantially distorted.

Thus, if no any sintering agent is added when the SiC—Si₃N₄ powder is sintered, the main oxidation products produced during sintering are SiO₂ and a little Si₂N₂O. Thus, the oxidation sintering reaction of the system progresses and Si₃N₄ is substantially oxidized. Typically, the amount of SiO₂ in the matrix of system is kept below a predetermined threshold value, since excess silica can degrade the durability of the sintered body. Erosion testing of the P1 sample in cryolite-sodium fluoride melt in an electrobath of aluminum demonstrated that the amount of silica was not in excess, as the sintered P1 sample still had the property of preventing penetration and melt wetting resistance characteristic of sintered Si3N₄/SiC composite materials.

The study on microstructure of Si₃N_—SiC—Si sintering system Sample P2 was analyzed by XRD and EPMA; the results are presented as FIGS. 10 and 11, and are of the surface (0-5 mm) and interior area (8-16 mm), respectively. As can be seen from FIGS. 10 and 11, metallic silicon is present in the sintered matrix of P2. The oxidation products of sintering are Si₂N₂O and a little SiO₂; the main crystal phases are hexagonal SiC and Si₃N₄. But compared with the X-ray patterns of the surface and inner area of P2, it can be seen that the content of crystal phase of Si₂N₂O and SiO₂ in the surface area (FIG. 10) of the sample are relatively high (compared with the peak strength). Metallic silicon still exists in the surface area (FIG. 10). There is relatively little Si₂N₂O crystal phase present in the inner area (FIG. 1) is little.

Electron microprobe analysis results for sample P2 are shown in FIGS. 12 and 13. Turning to FIG. 12, the surface area of P2 the distribution of metallic silicon, with the diameter of the silicon particles being less than about 50 cm; the metallic silicon particles are distributed in the among of coarse SiC particles, which indicates that metallic silicon in the surface area has not been disappeared totally after being sintered at the relatively high temperature of 1450 degrees Celsius. In addition, there is obvious chromatic aberration in the surface area along the pores extending below the surface (see FIG. 13). Comparison of the distribution of O, C and N indicates that the surface of the particles have an area of high oxygen content. Thus, the reaction of oxygen diffusing toward surrounding area occurs around the pores.

FIG. 14 illustrates the interior area (8-16 mm) morphology of sample P2, and shows that the content of metallic silicon in the inner area is relatively greater and concentrated in the voids of SiC. Such distribution appears to be beneficial to the oxidation resistance of SiC and thus improves the binding strength. Apparently, metallic silicon is melted into the SiC voids and acts as a binder.

FIG. 15 illustrates the Si₂N₂O mineral morphology in inner area (8-18 mm) of sample P2. Significant Si₂N₂O is present in the interior area of sample P2. Si₂N₂O is present on the surface of grains Si₃N₄ as short, cylinder crystals. Further, silica has precipitated in the surrounding area. Inner oxidation of pores is also be observed, and the oxidation process extends toward the sample interior along the void surface area. SiO produced by oxidation is precipitated onto the surface due to total oxidation of exterior surface, which prevents further oxidation. The Si₂N₂O crystal morphology is not as obvious, and the Si₂N₂O crystals seem to grow finer. So the ratio of remnant nitrogen is high and the strength of the sintered P2 sample was high as well. The X-ray pattern confirms the presence of Si₂N₂O. And it is probable that the oxygen diffused into the matrix reacts preferentially with metallic silicon.

So, the metal silicon (surface and inner area) in the sample matrix is not totally oxidation during the sintering of the SiC—Si₃N₄ sample. The metallic silicon apparently infiltrates into the void of the SiC crystals at the sintering temperature and acts in a binding role, likely as a plastic phase. Meanwhile, metallic silicon reacts more easily with oxygen than does Si₃N₄, so the formation of a Si₂N₂O phase is not observed, and thus more Si₃N₄ is present after the sample is sintered. The sample thus produced has better chemical durability characteristics, which were confirmed by the erosion test of cryolite-sodium fluoride melt test.

The Study on Microstructure of Si₃N₄—SiC—Si O₂ Sintering System

Sample P3 was analyzed by XRD and EPMA. FIGS. 16 and 17 show the exterior surface area and inner area XRD pattern for sample P3, respectively. Sample P3 was produced by sintering SiC—Si₃N₄ in the presence of SiO₂. The analysis sample P3 shows that the main phases are SiC and Si₃N₄, but the content of Si₂N₂O in the surface area of the binding phase is less than that of the inner area (comparison of peak strength). The SiO₂ phase in the surface area is relatively high (comparison of peak strength) compared to that of the inner area (significant amounts of SiO₂ were not observed in X-ray pattern). In addition, the primary peak of Si₂N₂O mineral was detected both on surface and interior of the P3 sample, indicating that the Si₂N₂O content was higher and SiO₂ may be present in an amorphous or glassy state; if so, the structure is suited for use in a thermal shock resistance environment.

FIG. 18 is surface EPMA pattern of sample P3; FIG. 19 is surface area Si₂N₂O morphology of sample P3; and FIG. 20 is interior area (8-16 m) morphology of sample P3. The analysis of FIG. 18 shows that the oxidation product of Si₃N₄ on the surface is Si₂N₂O and SiO₂, and the crystal grows very well (seeing FIG. 19). Meanwhile, Si₃N₄ here may be covered by SiO₂ and Si₂N₂O and thus cannot be detected. FIG. 20 shows that Si₂N₂O crystals from the oxidation of Si₃N₄ are very fine; this may be an effect of the speed of gas diffusion through the silica layer.

To sum, by sintering the product of SiC—Si₃N₄ in the presence of SiO₂, the process of oxidation in the surface area is relatively smooth, as the oxidation of Si₃N₄ is carried out in the presence of a superfine SiO₂ layer. The existence of the superfine SiO₂ layer reduces or prevents the gas diffusion, and makes the oxidation of Si₃N₄ in the body interior incomplete and thus the size of the remaining Si₃N₄ crystals/grains is typically fine and small. As a whole, Si₃N₄ in the interior portion of the SiC—Si₃N₄ sintered body containing the superfines of SiO₂ is at least partially oxidized and thus more Si₂N₂O biproduct is produced. The body has enhanced physical and mechanical properties. A body produced similarly to the P3 sample was thermally cycled in a tunnel kiln 220 times without cracking, a longer life than typical for SiO₂ bodies under the same conditions.

While the invention has been illustrated and described in detail in the drawings and foregoing description, the same is to be considered as illustrative and not restrictive in character. It is understood that the embodiments have been shown and described in the foregoing specification in satisfaction of the best mode and enablement requirements. It is understood that one of ordinary skill in the art could readily make a nigh-infinite number of insubstantial changes and modifications to the above-described embodiments and that it would be impractical to attempt to describe all such embodiment variations in the present specification. Accordingly, it is understood that all changes and modifications that come within the spirit of the invention are desired to be protected. 

1. A method of manufacturing a composite sintered body of silicon nitride and silicon carbide comprising: (a) mixing a predetermined amount of silicon nitride powder with a predetermined amount of silicon carbide powder to produce a resultant mixed powder; (b) heat-treating the resultant mixed powder at a temperature of between about 800 and 1500 degrees Celsius in a substantially nitrogen sintering atmosphere; (c) producing a thin film of silica around individual silicon nitride and silicon carbide grains; (d) retarding the diffusion of oxygen through the silica film; (e) retarding the oxidation of silicon nitride particles to produce silica and nitrogen gas; (f) substantially eliminating porosity from the compact; (g) sintering individual grains together; and (h) cooling the sintered body to yield a sintered substantially silicon nitride/silicon carbide body; wherein the substantially nitrogen sintering atmosphere has a finite and predetermined oxygen partial pressure; wherein the pressure of the substantially nitrogen sintering atmosphere is not substantially greater than atmospheric pressure; and wherein the combined heat-treating temperature and oxygen partial pressure of the sintering atmosphere minimizes the oxidation of silicon nitride while maximizing the sintering of the silicon nitride/silicon carbide body.
 2. The method of claim 1 wherein the sintering occurs at a temperature in the range of between about 800 degrees Celsius and about 1200 degrees Celsius.
 3. The method of claim 1 wherein the resultant mixed powder has a composition of about 85 weight percent silicon carbide and about 15 weight percent silicon nitride.
 4. The method of claim 1 wherein the resultant mixed powder has a composition of about 80 weight percent silicon carbide, about 15 weight percent silicon nitride, and about 5 weight percent silicon metal.
 5. The method of claim 1 wherein the resultant mixed powder has a composition of about 75 weight percent silicon carbide, about 15 weight percent silicon nitride, and about 10 weight percent silicon dioxide.
 6. The method of claim 1 wherein the sintered body is substantially comprised of grains of silicon carbide distributed in a Si₂N₂O matrix.
 7. The method of claim 1 wherein the sintered body is substantially comprised of grains of silicon carbide and grains of silicon nitride distributed in a Si₂N₂O matrix.
 8. The method of claim 1 wherein the sintered body 6 wherein the silicon carbide grains have a thin outer layer of silicon dioxide.
 9. The method of claim 1 wherein the substantially nitrogen sintering atmosphere is air.
 10. (canceled)
 11. (canceled)
 12. (canceled)
 13. (canceled)
 14. (canceled)
 15. (canceled)
 16. A method for making a SiC/Si₃N₄ sintered composite body, comprising: a) forming a green body of a mixture of SiC powder, Si₃N₄ powder, and a third silicon-containing powder; b) heating the green body to a temperature of between about 800 and about 1450 degrees Celsius in a low oxygen partial pressure atmosphere; c) forming a silicon-containing liquid throughout the body; d) infiltrating substantially all open porosity with the silicon-containing liquid; e) partially oxidizing Si₃N₄ grains to form SiO₂ and nitrogenous byproducts; f) sintering the green body to form a sintered body comprising SiC and Si₃N₄ grains; and g) forming a substantially silica layer around the SiC and Si₃N₄ grains; wherein the mixture of SiC powder, Si₃N₄ powder, and a third silicon-containing powder includes SiC and Si₃N₄ present in a weight ratio of between about 4:1 and about 7:1.
 17. The method of claim 16 wherein the third silicon-containing powder is selected from the group consisting of silicon metal, silica, and mixtures thereof.
 18. The method of claim 16 wherein the low oxygen partial pressure atmosphere is air.
 19. The method of claim 16 wherein the low oxygen partial pressure atmosphere is substantially nitrogen.
 20. The method of claim 16 wherein the low oxygen partial pressure atmosphere is characterized by a small but finite oxygen partial pressure.
 21. A method for making a substantially densified SiC/Si₃N₄ body, comprising: a) mixing SiC grains, Si₃N₄ grains, and a third silicon-containing powder to produce an admixture; b) forming a green body from the admixture; c) heating the green body to a temperature of between about 800 and about 1450 degrees Celsius in a low oxygen partial pressure atmosphere to produce a heated body; d) coating substantially all of the SiC and Si₃N₄ grains with respective substantially liquid silica films; and e) cooling the heated body to yield a densified body comprising SiC and Si₃N₄ grains; and wherein the mixture of SiC grains, Si₃N₄ grains, and a third silicon-containing powder includes SiC and Si₃N₄ present in a weight ratio of between about 4:1 and about 7:1.
 22. The method of claim 21 and further comprising f) infiltrating substantially all open porosity of the SiC grains with a silicon-containing liquid.
 23. The method of claim 21 wherein the substantially liquid silica films function to slow the diffusion of oxygen to the respective grain surfaces to prevent complete oxidation of the grains while the body is heated.
 24. The method of claim 21 and further comprising g) disposition of Si₂N₂O crystals on the Si₃N₄ grains. 